Method to carry out strongly exothermic oxidizing reactions in pseudo-isothermal conditions

ABSTRACT

Method and apparatus for carrying out highly exothermic catalyzed reactions, like so-called oxidative reactions, in pseudo-isothermal conditions, for example the reaction for producing nitric acid and the reaction for producing formaldehyde.

In its most general aspect the present invention refers to a method forcarrying out exothermic chemical reactions in pseudo-isothermalconditions.

In the rest of the description and in the subsequent claims, with theterm pseudo-isothermal conditions we mean to indicate those conditionsin which the reaction temperature is controlled in a limited range ofvalues around a predetermined optimal value.

In particular, this invention concerns a method for carrying out, inpseudo-isothermal conditions, highly exothermic catalyzed reactions,like oxidative reactions, for example ammonia oxidation to give nitricacid and methanol oxidation to give formaldehyde.

The present invention also refers to an apparatus for carrying out theaforementioned method.

PRIOR ART

Regarding highly exothermic oxidative reactions it is well known that,in order to avoid clearly dangerous operating conditions, it is requiredto control one or more operating variables, like reaction temperatureand concentration of at least one reactant.

Thus, for example, in the production of formaldehyde through methanoloxidation, the high concentration of the reactants and the highexothermicity of the reaction quickly lead to operate in explosiveconditions; from here arises the need to strictly control both theconcentration of the reactants and the reaction temperature belowwell-determined values.

Moreover, when the reaction temperature and concentration of thereactants exceed said values, there may happen phenomena of “poisoning”and degeneration of the catalyst, with the consequent inevitable yieldreduction. This is the case of ammonia oxidation to give nitric acid,where the catalyst based upon Co₃O₄ undergoes a rapid CoO reduction, amuch less active form of Co₃O₄, right when the concentration of thereactant exceeds a predetermined threshold at a predeterminedtemperature.

To control the temperature and the concentration of the reactants, ithas been suggested to carry out the reactions of the considered type influid bed reactors.

This type of reactor, however, suffers from many recognized drawbacks,such as excessive energy consumption caused by the need to feed largequantities of air so as to keep the ammonia concentration below theexplosivity threshold, greater constructive complexity with respect tofixed bed reactors and problems of dust recovery.

Moreover, the catalyst in movement inside said fluid bed reactorscarries out a corrosive action against the walls of the reactorsthemselves.

SUMMARY OF THE INVENTION

The technical problem underlying the present invention is that ofproviding a method for carrying out highly exothermic oxidativereactions, in pseudo-isothermal conditions, between reactants fed incontinuous flow to a predetermined catalytic bed, capable of overcomingthe aforementioned drawbacks with reference to the prior art, in otherwords to operate below explosivity limits of the mixtures of reactantsand of reactants-products and to promote a longer lifetime of thecatalyst.

The aforementioned technical problem is solved, according to the presentinvention, by a method characterized in that at least part of saidcontinuous flow of reactants is fed at different points of saidcatalytic bed corresponding to different successive stages of thereaction, at respective different predetermined temperatures andflow-rates, where the concentration of the reactants is low.

In the non-limiting case of use of a pseudo-isothermal reactor with avertical axis, with a catalytic bed crossed axially by the reactants,the successive stages of the reaction are defined at differentrespective heights in the catalytic bed, wherein the reactants are fedat the predetermined flow-rates and temperatures.

The characteristics and advantages of the method of the presentinvention shall become clearer from the following description of anexample embodiment thereof, made with reference to the attached drawingsgiven for indicating and not limiting purposes.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically shows a chemical reactor for carrying out themethod according to the invention;

FIG. 2 schematically shows an enlarged view of a detail of the reactorof FIG. 1.

DETAILED DESCRIPTION OF THE FIGURES

With reference to FIG. 1, a chemical reactor, with a vertical axis, usedto carry out highly exothermic reactions, for example and preferablyoxidative reactions like ammonia oxidation to give nitric acid, isglobally and schematically indicated with 1.

Said reactor 1 comprises a cylindrical shell 2, opposite end plates,lower 3 and upper 4. The upper end plate 4 is equipped with a manhole 5,whereas the lower end plate 3 is equipped with an opening 6 fordischarging the reaction products.

In said shell 2 a reaction zone 7 is defined, representatively situatedbetween a lower line 8 and an upper line 9, to receive a predeterminedcatalytic bed (L), intended to be crossed axially by the reactant gasesand by the reaction products.

The catalytic bed (L) is supported in a per se known way and thereforeit is not represented.

In the catalytic bed (L) a plurality of heat exchangers 10 and acorresponding plurality of distribution-supplier devices 12 are immersedand supported; said heat exchangers 10 are plate-shaped, rectangular,preferably arranged radially, in many rows concentric and coaxial tosaid shell and with long sides 11 parallel to the axis of the shellitself.

In accordance with a characteristic of the present invention, andaccording to a preferred embodiment, with each exchanger 10 isassociated, in particular is fixed, a couple of distribution-suppliers12, for which it constitutes an appropriate support, as shall becomeclear from the rest-of the description.

In particular, with reference to FIG. 2, each heat exchanger 10comprises a wall 27 and a wall 28, juxtaposed, joined at the perimeter,for example through appropriate welding, in a mutually distancedrelationship, so as to form a first chamber 18 between them.

Near to a side 11 of said exchanger 1 and through a welding line 25,having a portion 32 parallel to said side 11 and a portion 33perpendicular to it, between said walls 27 and 28 a second chamber 19 isalso defined, separated fluid-tight from said first chamber 18.

The chamber 18 is equipped with an inlet fitting 29, and with an outletfitting 31, whereas the chamber 19 comprises only one inlet fitting 34.

Two box-shaped carters 20 and 22 are fixed to the wall 27 of eachexchanger 10, extending perpendicularly to said side 1 for the wholewidth of the respective exchanger 10.

The carters 20 and 22 define with the wall 27 respective ducts 21 and23, in fluid communication, on one side, with said second chamber 18through openings 36 and 37, formed in the wall 27 and, on the otherside, with the outside of the exchanger 10, and therefore with thecatalytic bed (L) in which said exchanger 10 is immersed, through aplurality of holes 26, formed in the carters themselves.

Preferably, said holes 26 are arranged in rectilinear alignments,extending longitudinally to the respective carter (20, 22).

The carters 20 and 22, supported by a respective exchanger 10,essentially constitute a distribution-supplier device 12 for apredetermined fluid, fed to said carters through the chamber 18.

The plurality of exchangers 10 with relative distribution-suppliers 12,constitutes, in accordance with the present invention, an apparatussuitable for controlling the temperature and the concentration of thereactants in the catalytic bed (L), as shall become clear in the rest ofthe description.

The reactor 1 also comprises:

-   -   feed ducts for the predetermined reactants (13 and 14) which are        in fluid communication with the chamber 18 and 19 respectively        of each exchanger 10, through a system which includes ducts (15        and 16) and respective fittings (30 and 35).    -   collector ducts 17 for the reaction products, which are in fluid        communication, on one side, with the outlet fittings 31 of each        exchanger and, on the other side, with a central duct 24 axially        provided in the reactor.

With reference to the aforementioned apparatus, the method of thepresent invention for carrying out highly exothermic oxidative reactionsin pseudo-isothermal conditions, through simultaneous control of thereaction temperature and of the concentration of reactants aroundrespective predetermined values, shall now be described.

A flow of reactants, for example ammonia and oxygen for the productionof nitric acid, is continuously fed to the reactor 1, and is separatedinto two parts upon entry.

A first part or main part of said flow is preheated to the mostappropriate temperature to trigger the desired reaction (ammoniaoxidation) through heat exchange with the catalytic bed (L); for such apurpose and in the specific case illustrated, said main part of the flowof reactants is divided, through the distributor 12, between all of theducts 15—fittings 30, for feeding the chambers 18 of all of theexchangers 10.

Exiting from the plurality of exchangers 10, the reactants thuspreheated are collected by the collector 20, which conveys them to thelower end of the central duct 24. Exiting from the upper end of saidduct 24, the preheated reactants are distributed above the catalytic bed(L), crossing which they start off the desired highly exothermicoxidation reaction.

A second part of said flow of reactants, or control flow, is dividedbetween all the chambers 18 of the plurality of exchangers 10, from eachof which it is fed to the respective pairs of distribution-suppliers 19,20.

As described above, said distribution-suppliers 19, 20 are positioned inthe catalytic mass of the bed (L), at heights strictly corresponding tothe stages of the reaction taking place in correspondence of which it isforeseen to control the concentration and temperature of the reactants.

In accordance with the present invention such a control is substantiallymade possible by the injection in predetermined points of the catalyticbed of a fresh flow of reactants, the concentration of which isregulated continuously adjusting suitably and in a per se known way theflow rate of the second part of said flow of reactants.

The reaction products are discharged from the reactor 1 through theopening 6.

The invention thus conceived is susceptible to variants andmodifications, all of which are covered by the scope of protection ofthe present invention defined by the following claims.

1. Method for carrying out highly exothermic oxidative reactions inpseudo-isothermal conditions, between reactants fed in continuous flowto a predetermined catalytic bed, characterized in that at least a partof said continuous flow of reactants is fed at different points of saidcatalytic bed corresponding to different successive stages of thereaction, at respective different predetermined temperatures andflow-rates.
 2. Method for carrying out highly exothermic oxidativereactions in pseudo-isothermal conditions, between reactants fed in acontinuous flow to a predetermined catalytic bed, in which a pluralityof heat exchangers is immersed and supported, wherein: a plurality ofdistribution-suppliers is positioned in said catalytic bed, at differentpoints thereof strictly corresponding to different predetermined stagesof said oxidative reaction, said continuous flow of reactants is dividedinto a first part or main flow and a second part or control flow with apredetermined temperature and flow-rate, said first part or main flow ispreheated through heat exchange with said catalytic bed feeding itthrough said plurality of exchangers, said main flow of preheatedreactants is recovered and it is fed continuously to said catalytic bed,and said second part or control flow is fed to said plurality ofdistribution-suppliers to inject respective fresh flows of reactants ata predetermined temperature and flow-rate into the catalytic bed. 3.Apparatus for carrying out a highly exothermic oxidative reaction inpseudo-isothermal conditions according to the method of claim 1,comprising a plurality of heat exchangers wherein with each of saidexchangers is associated at least one distribution-supplier suitable forbeing fed continuously by a flow a reactants at a predeterminedtemperature and flow-rate.
 4. Apparatus according to claim 3, whereinsaid at least one distribution-supplier is supported fixed by saidrespective heat exchanger.
 5. Apparatus according to claim 4, whereinsaid heat exchanger is plate-shaped and substantially rectangular,inside which a first chamber, intended to be crossed by a respectiveflow of reactants to be preheated, and a second chamber, separatedfluid-tight from said first chamber and in fluid communication with saidat least one distribution-supplier are defined.
 6. Apparatus accordingto claim 5, wherein said distribution-supplier comprises a carter fixedto a wall of a respective plate-shaped heat exchanger, with which itsubstantially defines a duct in fluid communication, on one side, withsaid second chamber of the exchanger and, on the other side, with theoutside of the exchanger itself, through a plurality of holes formed insaid carter.
 7. Reactor for carrying out highly exothermic catalyzedoxidative reactions in pseudo-isothermal conditions, comprising a shellin which is defined a reaction zone at least partially occupied by acatalytic bed wherein it comprises an apparatus according to claim 3,immersed in said catalytic bed.